Process for zinc smelting



Jan. 10, 1950 c. w. MORRISON y PROCESS FOR ZINC SMLTING 3 Sheets-Sheet 1 Filed April 2,. 1947 QNVNYS NQM usw@ w INVENTQR L BY www@ ATTORNEYS Jan. l0, 1950 c. w. MORRISON PROCESS FOR ZINC SMELTING 3 Sheets-Sheet 2 Filed April 2, 1947 AN EN M mw. mm

INVENTOR Cjfll /UW ,@L, MJ USMS ATTORNEYS Jan. l0, 1950 c. w. MORRISON 2,493,823

PROCESS FOR ZINC SMELTING Filed April 2, `1947 3 Sheets-Sheet 3 26 7b ww//VG Ecc/Es GA s 5 HOLDER INVENTOR ATTORNEYS l aceous material.

Patented Jan. 10, 1950 l UNITED STATES PATENT CFFICE PROCESS FOR ZINC lSMELTING Clyde W. Morrison, Bartlesville, Okla., assignor to National Zinc Company, Inc., New York, N. Y., a corporation of New York Application Aprll 2, 1947, Serial No. '138,981

This invention relates to zinc smelting and has for its object the provision of an improved method of smelting zinc ores and other suitable zincbearing materials, particularly for the production of slab zinc.

Slab zinc is commonly produced by heating and smelting a mixture of zinc oxide and vcarbon in a reaction chamber from which free oxygen and other oxidizing agents are excluded during the reaction period. The zinc oxide may be a constituent of roasted zinc concentrates, naturally oxidized zinc ores, by-products of metallurgical or chemical operations, or other suitable zinc-bearing materials. The carbon may be va constituent of coke, coal, charcoal or other suitable carbon- Zinc vapor and carbon monoxide gas are produced as the end products of the reaction, and are delivered to a condenser where the zinc vapor is condensed to molten zinc and the carbon monoxide exhausted or, ,if desired, recovered for subsequent use. The molten zinc lis appropriately withdrawn from the condenser and cast into slabs.

In accordance with the presentinvention, Zinc smelting is carried out 'in a battery of reaction chambers generally resembling any one of the present day types of by-product coke oven batteries or furnaces. Combustion chambers, heating flues and heat regenerators are operatively associated with the reaction chambers, as in Aa cokeoven battery. A zinc condenser is directly connected to each reaction chamber. The gas outlets of the condensers are connected to a dust and fume recovery unit, and a gas lholder is provided for the collection and storage of carbon monoxide gas.

One of the novel features of thel invention resides in passing hot .carbon monoxide gas free of all or nearly all oxidizing constituents through each idle condenser during the periods that its .retort is being discharged and recharged. Another novel feature resides in passing a substantial volume of such hot carbonmonoxide gas through the charges undergoing smelting in the retorts, and preferably, from time to time during the smelting operation, adding granular carbonaceous material on top of the charges undergoing smelting. The -hot carbon monoxide gas is derived from the condensers in which .zinc vapor is condensed, and

may be heated and vfreed o'f all .or nearly all .oxi-

Fig. 1 is a top plan, somewhat diagrammatic, of`

an apparatus for ,practicing the invention,

Fig. 2 is a front elevation, vpartly in section,` oi

the apparatus,

6 Claims. (Cl. 'l5-486) Fig. 3 is a transverse sectional elevation, somewhat diagrammatic, through an ore retort orreaction chamber, and

Fig. 4 is a transverse sectional elevation, similarly somewhat diagrammatic, through a coke retort.

The zinc smelting furnace illustrated in the drawings is constructed generally along the lines of a by-product coke oven battery, and has aplurality oi yexternally-heated reaction chambers `or retorts Il! in which the zinc ore or other zinc-'bearing material is smelted, andthe retorts are hence designated ore retorts on the accompanying drawings, `and are hereinafter generally referred to as smelting retorts, `Combustion or heating chambers ll l are arranged between the retorts l0. Preheated fuel gas and air Iare admitted to the bottom of each heating chamber H through `ports l2 and i3, respectively. Heatregenerators Mfand I5 Aare operatively associated with the chambers il, andare operated as customary for alternately absorbing heat from the exhaust gases from the chambers l I and lfor preheating the iuel gas Land air. The main structural features of the-apparatus -form no part of the invention except insofar as modified for practicing the zinc smelting meth-v vmay -be lconsideredl as about 40 reet long, 12 feetv high and l5 inches wide, and the'condensers i8' as about -4 feet long, 119 feet 'high and l5 inches wide, all inside dimensions. The battery oi retorts -Hl is built in a 'furnace structure 4of refractory and insulating brickwork with structural steel supports, like a 'conventional coke oven rurnace; and the condensers :are built lof refractory and'insulating material with -such heat-dissipating characteristics as are required for leconomic` condensation "of lzinc vapor within Aeach condensing chamber.

The gas #outlet 2l of 'each condenser yis provided with afvalve '22, and all the outlets are connected'-to*a commoniiue or mani-fold '-23 discharging into a dust chamber V2"4 or other suitable dust and fume recovery unit. The gas, mainly carbon monoxide, is drawnthrough the dust collector by a-gas pump 'or'ian 2'5 'and delivered vvto va gas holder or 'storage tank 2B'. Arrows -on` the 'drawings indicate the 'direction of flow of carbon monoxide vgasth'roughout"the apparatus.

The condenser-s1 ternally heated, like the smelting retorts, and are i of the same dimensions, but are not connected to Y a condenser. the gas holder 26 throughqa pipe 2,8 rhaving` a Carbon monoxide gas, drawn from valve 29, enters the front end 'of each Ycoke retort 2'I through a port or ports 28 in the side/wall or bottom thereof, and passing through the heated coke is deprived of all or nearly all oxidizing constituents and raised to a predetermined tempera.-

ture. The resulting hot carbon monoxide gas -passes through a port 30 in the roof near the rear ofthe coke retortto rajheat-insulated.distributingr flue or pipe 30, 'from`whence` hergas is drawn, 1

asrequired, through insulated pipes 37|' having valves ,32 into the ducts Vorv 4flues I9 and thence *Y through these ducts or iiues into the condensers I8.- @ther insulated pipes 33Mhaving valves 34 conveylhot carbon monoxide gas from the distributingflue 30, through-a portor ports 33 in the sideQWall or bottomlof eachvsmelting retort, into each smelting retort. v l 'y The carbon'monoxide gas in the holder 26 may bemaintained under sucient pressure to force the gas'through the cokeretorts 21, distributing fluev 3D etc., or a, gas pump or fan 35 may be provided-for that purpose. A pipe 36 having a valve 3'!V is also connected tothe gas holder 26 for conveying Ycarbon monoxide gas to the burning flues for the heating chambers I`I. Under normal operatingponditions, allV of, :the carbon monoxide generated in the smeltingY operation is collected in the gas holder 25,; and there is thus provided adequate carbon .monoxide for introduction into the smelting ,retorts Aand condensers, as hereinafter described-.fand the `4exeess. carbon monoxide is available for delivery (through the pipe 36V) to the fuel gas for firing the heatingl chambers II.

Since the hot coke in the coke retort (or retorts) 2l is gonly consumedin removing by deoxidation any `.oxidizingconstituents inthe carbon monoxide gas, theactual consumption ofi coke in this retortvis relatively small. From timeto time, as

required, fresh coke may be added to the retort through openingsV 38 in the top of the furnacev structure.- y The coke is conveniently delivered to the charginglopenings inthe top ofthe retort by doublefgate chutes 39ofrconventional construc-A tionf, toprevent the escape of,v carbon monoxide gas. The coke retortmay-be cleaned of residual ash., when necessary, byl removing the endV doors '5f-'ami 'I'nd pushing the ash out into a dump car or'the like.

. hebattery of smelting retorts I I) operates as a wholesin la substantially continuous manner, al-

thoughsmelting in each individual retort is ane-O;

intermittent or batch operation The retortsl are charged/through their top openingsB with a mixture of zinc-bearing and carbonaceous ma-Y terials.A Sinteredzinc 'ore containing about 70% zinc, along with skimmings blue powder and other by-produetsrof` the operation mayconstitute the zinc-bearing material;

inch to one inch. The carbonaceous material may be coke containing-80-85% xed carbon'and Y crushed to a particle size varying from one-eighth ployed for conveying the mixture from storage Y The sinter is preferably crushed to a particle size varying from one fourth 4 bins to the charging lopenings 38, and a leveling tool is used to level the mixturein the retorts and to suitably lill them, After a retort has been lled With the smelting mixture, the openings 38 are closed and sealed. During charging (and subsequent discharging) the valve 34 is closed, and when the retort is charged and the openings 38 sealed, the valve 34 is opened and hot carbon monoxide gas is introduced into the front end of the retort. With retorts of the size hereinbefore suggested, carbon monoxide gas may advantageously be introduced at the rate of from 25 to 150 cubic feet per minute (calculated at 0 C. and a pressure of '760 mm. mercury). More generally and in terms of the vhot gas,.the volume of .hot carbon monoxide gas introduced into each smelt- Iing retort per minute maybe from 1/8.to A the volume of the retorti, j Y i The oW of carbon monoxide gas through .the retort, as smeltingl progresses, accelerates,V by convection gas currents, the transfer of heat from the heatedfwalls of the retort vto .the interior 'ofV the smeltingv charge. The carbon monoxide Afur' ther, by chemical reactiomaccelerates the reduc-v Y introduced into the retort throughv the.' top charg ing openings 38,4the double-'gate chutes. 39 preventing the escape of carbonmonoxideand ,zincv Vapor during vthev charging of such-cok e..rThe added quantities of coke iillthesjpace progressivelyivacated in the retortjby the evolution of carbon monoxide and Zinc vapor from the charge,v and overlay the charge asit',,is'workedfoff.-Y overlying layer of hot cokeis anadditional pro?-v tection against reoxidation ofzinc vapor, and 'also' serves to lter out' objectionable fume Whose entrance into the condenser might excessivelycontaminate the slab zinc,`product. j

During the smelting operation in each retort', the zinc Vapor and carbon monoxide gas evolved from the charge together with thelcarb'onmon-V oxide gas introduced through 'the pipe33 pass' through the duct I9 into the condenserwhere the zinc vapor iscondensed to'molten'zinc and the carbon' monoxide gas ows through the'outlet 2| to the dust collector, etc. From 'time to time,

or continuously, if desired, molten. zinc is' withdrawn through the tap-holeA 20 of the condenserA into a holding furnace or other appropriate reserdenser has an opening in alignment With the ilue I9.an d normally closed byaplng il `for permit--` ting access to the flue forfcleanin'g, etc., when' necessary. The furnace Vor batteryY ofY retortsY is continuously fired' as in ,by-product''coke-ovenpractice. Natural gas, producergas or other suitable gaseous fuel is usedfor iiring,V supplemented. byv carbon monoxide gasproduced by the smelt;

ing reaction in the retorts;

The Working-off ofv the charge may take around 24 hours. vThe charging and discharging of the individual retorts takes place, in sequence over the Working-off period, so. as"

to maintain `continuity 'of operation oftheiba/t-` tery as a Whole. When a retort is'vvorked-oi,l

. inV each retort aal-asma that is when: the smeltingl off the charge in that retort is concluded, the valve u is closed, and the. valve 32 is openedv to permit the. now of hot carbon monoxide gas from the pipe 3i through the duct` i3. andthe condenser-during discharging andl subsequent charging ciy the. retort. At the same., timeA a gate. onvalve 4U in the duct I9 is closed to prevent air` or other oxidizing agent entering the duct-andcondenser-during discharging and rechargingY ofthe retort. 'Ehe gate-Ml. is positioned as near as practical, to the, inlet end of the dut la, and the pipe 3 l connected to the duct as nearas practical to the gate `4l), in order. to,k keep the duct, asytelkas the condenser, het and freeof oxidiznacenstitaents- Thedoors lli-and ll are rernoyed, andthe residue or worked- Ofi Charge-is. pushed. out i the retort by' a mechemical ram into a, carresidue., particuany where @one is added te; th Lretort from. time to time during smelting, contains a substantial amount of recoverable carbon, which may be separated from the residue for reuse in the smelting operation. The doors I6 and I1 are then replaced, and the retort recharged as hereinbefore described. The valve 34 is then opened and hot carbon monoxide gas begins to now into the retort. During discharging and recharging, the retort continues to be externally heated by the adjacent heating chambers, and the highly heated retort and the hot carbon monoxide gas promptly brings the charge up to the smelting temperature of around 1100 C. Alternatively, the charge may be brought up to about the smelting temperature in the hot retort before opening the valve 34. Until the charge attains the smelting temperature, gases from the retort are bled out through the charging openings 38. When the charge in the retort reaches the smelting temperature, the gate 40 is raised to open the duct I9, the valve 32 is closed, and smelting progresses with condensation of zinc Vapor and recovery of carbon monoxide as hereinbefore described.

The gaseous products of the smelting operation (zinc vapor and carbon monoxide) leave the retorts at about the smelting temperature (1050-1200 C.). For eilicient condensation of zinc vapor, the condensers are maintained at an operating temperature of about 550 C. The necessary dissipation of heat from the condensers to maintain this operating temperature is attained by constructing the condensers of refractory materia] of good heat conductivity, and, if necessary, by artificial cooling. One of the important aspects of the present invention resides in maintaining Within all of the condensers at all times a minimum temperature of around 550 C. and a non-oxidizing atmosphere, thereby inhibiting the formation of objectionable by-products, such as blue-powder, crusts and a-ccretions, in the condensers and their connecting ducts and flues. Thus, in accordance with the invention, hot carbon monoxide gas flows through an idle condenser and its associated duct at a precisely controlled rate during the periods that its retort is being discharged, recharged and the charge brought up to the smelting temperature. The carbon monoxide gas is derived from the smelting operation, and is heated to near the smelting temperature (say about 10000 C.) and freed of all or nearly all oxidizing constituents by passage through the coke retort. The rate of flow of the hot gas through the idle condenser is controlled by the valve 32 to maintain the contemplated minimum temperature within that condenser. During the periods that a condenser is idle, any

I denserl (or: condensers); I gas, While it may fluctuate. somewhat. amount 6. artificial cooling thereofis interrupted, and the normal operating heat dissipation or: the condenser may', if desired, be further decreased by providing the condenser duringv Such idle periods with temporary. heat insulation, thereby lowering thev rate of flow of; the. hot carbon monoxide, gas required to maintain the contemplated minimum temperature within the condenser. The carbon monoxidegas passes out of the. condenscrthrough the outlet iv (the tap-hole 2B. beingv closed) into the. flue 23., as in the normal operation ofi the condenser.

The. yfurnace; battery: of retorts,'may includev one or more colse retorts, depending upon. thev number of smelting retorts in the battery. The amount of. carbon monoxide, gas: flowing through the coke retort (or retorts) isy controlled by the valve 25 to. meet, the carbon monoxide requirements of the smelting retorts andl the. idle con- This carbon monoxide from time to time, is in constant circulation through the smelting retorts, the idle condensers, dust collector, gas holder and coke retorts. None of this carbon monoxide gas is intentionally consumed in process, and hence, aside from the inevitable losses, its quantity remains substantially constant for all practical purposes. Thus, practically all of the carbon monoxide evolved in the course of the smelting operation is available as fuel for firing the heating chambers Il. The amount of carbon monoxide gas currently flowing to the burning flues is controlled by adjusting the valve 31.

I claim:

1. The improvement in smelting zinc-bearing material in a battery of externally heated retorts connected to individual zinc condensers in which the individual retorts are operated intermittently While the battery of retorts as a whole is continuously operated, which comprises closing the connection between a retort and its condenser and passing hot carbon monoxide gas through the condenser during the periods that the retort is being discharged, recharged and the charge brought up to smelting temperature.

2. The improvement in zinc smelting according to claim 1 in which the hot carbon monoxide gas is derived from the condensers in which zinc vapor is condensed and the gas is passed through highly heated coke in one ofthe externally heated retorts of the battery.

3. The improvement in smelting zinc-bearing material in a battery of externally heated retorts connected to individual zinc condensers in which the individual retorts are operated intermittently while the battery of retorts as a whole is continuously operated, which comprises maintaining an idle condenser, during the periods that its retort is being discharged and recharged, at approximately its operating temperature for condensing zinc vapor by continuously passing hot carbon monoxide gas through the condenserA during such periods.

4. The improvement in smelting zinc-bearing material in a battery of externally heated retorts connected to individual zinc condensers in which the individual retorts are operated intermittently While the battery of retorts as a whole is continuously operated, which comprises maintaining an idle condenser, during the periods that its retort is being discharged and recharged, at approximately its operating temperature for condensing zinc vapor by passing carbon monoxide gas through highly heated coke and continuously 7. passing. the'resulting hot carbon monoxide gas through the condenser during such periods.

5. The improvement in smelting zinc-bearing material in a battery of externally heated retorts conected to individual zinc condensers in which the individual retorts are operated intermittently While the battery of retorts as a whole is continuously operated, which comprises passing hot carbon monoxide gas through the charges undergoing smelting in the retorts, withdrawing such carbon monoxide gas from the retorts along with the gaseous products of the smelting operation, from time to time during the smelting operation adding granular carbonaceous material on top of the charge undergoing smelting in the retorts, and maintaininganidle condenser, during the periodsthatfits retort is being discharged and recharged at approximatelyV its operating temperature for condensing zinc vapor by continuously passing hot carbon monoxide gas through the `condenser during such periods.

REFERENCES crrED The following references 4are of record'in the le of this patent:

UNITED STATES PATENTS Number Name Date 383,202 l Westman'- May 22, 1888 1,308,879j` Thomson July 8, 1919 1,733,500 Koppers Oct. 29, 1929 1,815,260 -Kemmer July 21, 1931 42,096,779 .Bartholomew et al. Oct. 26, 1937 

1. THE IMPROVEMENT IN SMELTING ZINC-BEARING MATERIAL IN A BATTERY OF EXTERNALLY HEATED RETORTS CONNECTED TO INDIVIDUAL ZINC CONDENSERS IN WHICH THE INDIVIDUAL RETORTS ARE OPERATED INTERMITTENTLY WHILE THE BATTERY OF RETORTS AS A WHOLE IS CONTINUOUSLY OPERATED, WHICH COMPRISES CLOSING THE CONNECTION BETWEEN A RETORT AND ITS CONDENSER AND PASSING HOT CARBON MONOXIDE GAS THROUGH THE CONDENSER DURING THE PERIODS THAT THE RETORT IS BEING DISCHARGED, RECHARGED AND THE CHARGE BROUGHT UP TO SMELTING TEMPERATURE. 